Rational Design and Mechanical Understanding of Three-Dimensional Macro-/Mesoporous Silicon Lithium-Ion Battery Anodes with a Tunable Pore Size and Wall Thickness

Silicon is regarded as one of the most promising next generation lithium-ion battery anodes due to its exceptional theoretical capacity, appropriate voltage profile, and vast abundance. Nevertheless, huge volume expansion and drastic stress generated upon lithiation cause poor cyclic stability. It has been one of the central issues to improve cyclic performance of silicon-based lithium-ion battery anodes. Constructing hierarchical macro-/mesoporous silicon with a tunable pore size and wall thickness is developed to tackle this issue. Rational structure design, controllable synthesis, and theoretical mechanical simulation are combined together to reveal fundamental mechanisms responsible for an improved cyclic performance. A self-templating strategy is applied using Stöber silica particles as a templating agent and precursor coupled with a magnesiothermic reduction process. Systematic variation of the magnesiothermic reduction time allows good control over the structures of the porous silicon. Finite element mechanical simulations on the porous silicon show that an increased pore size and a reduced wall thickness generate less mechanical stress in average along with an extended lithiation state. Besides the mechanical stress, the evolution of strain and displacement of the porous silicon is also elaborated with the finite element simulation.